Polymers of trifluoroethylene and process for obtaining them



r iettedoee UNITED STATES v 'mlngto'n, .Del., .asslgnors to E. '1. tin Pont-de Nemonrl' & Company, Wilmington; Del. a cor- 'poration of Delaware N6 Drawing, Application September-:19, m4,

. er ial No. 554,861

' l 3 Claims. (01.260-801 This.invention 'relates'to new compositions of '..with 250 parts of deoxygenated water and 0.3

vmatter and. more particularly to polymeric. part of ammonium persuli'ate. The reactor is materials. 1 closed, evacuated, cooled in a solid carbon d l- This case is a continuation-in-part of our 941- oxide-menthanol mixture, and is then further plication Serial No. 510,965 filedNovember l9, 5 charged with '10 parts-of trifluoroethylene and 1943, now Patent No. 2,419,009. f 75 parts of tetraiiuoroethylene. The reactor is In the above mentionedapplication, we have agitated and heated to 60 C. and thepressure disclosed valuable'polymeric products obtained in the reactor is then raised to 1750 lbs./sq. in. by polymerizing vinyl fluoride with other poly- The temperature is maintained at 58-68 C. dur- -merizable ethylenically unsaturated organicco ,ihg 9 /2 hours and additional deoxygenated water pounds, including trifluoroethylene, in the pi is periodically added so as to maintain a pressure ence of various polymerization catalysts, within the range of 800-1750 lbs/sq. in. The have HOW-found that p lymers of speci l. sum.of the individual pressure drops during the utility are obtained from trifluoroethylene either period between repressuring operations over 9.5

alone in-a xt With ylfi de rfother hours: is 2200 lbs/sq. in. The reaction vessel unsaturated organic compounds when thepolyis cooledgto room temperature, the unreacted merization is carried out in the presence-of. a :-portion ofv the gaseous .monomers is bled off and D r xy catalyst. the contents of the reaction tube are discharged.

This invention has as an object the'production t r drying, 74 parts of t m et m t g 0f new and useful compositions of matter. A fluoroethylene copolymer are obtained Films further object is the preparation of valuable high prepared by t. pressing t polymer b t molecular w t po y e s c p is n t flu osteel. plates covered with aluminum foil at ethylene. O h Objects l ppear hereinafter. 370-380 C. and 12,000 lbs/sq. in. haye tensile The practice of the invention is illustrated in t th of 1 50 1 i d elongations of the 'following examples in which the parts are by 204%, The temperature t which films possess weight a zero tenacity is 327 C. At a temperature of Example I 400 C. the copolymer can be extruded into con- A silver-lined high pressure reactor is flushed unuous filaments under an applied Pressure of with oxygen-free nitrogen and then is charged lbsJsq- Fnms of the copolymer had a with 300 parts of deoxygenated water. and 03 power factor loss of 0.0036 and a dielectric conpartof benzoyl peroxide; The reactor is closed, stant 0f cooled in a solid carbon dioxide-methanol mix- A Particularly valuable application of this ture and evacuated, and is then further charged vention is the successful production of polymers with 25 parts f t iflu oethyle e The reactor consisting essentially of trifluoroethylene, a1- is agitated and heated to 80 0. and the pressure though useful Polymers are Obtained from in the reactor is then raised to 4000 lbs/sq. in. tures of trifluomethylene and another Poly vby the injection of deoxygenated water The merizable compound containing at least 5% ,based temperature is maintained at 80 C. and addion the Weight of the m1XtuE'B, of the tllfluom" tional deoxygenated water is introduced as often ethyleneas required to maintain a pressure within the 40 The Polymerizable compounds other than the range of 30004000 m h sum of the trifiuoroethylene mentioned herein are the unindividual pressure drops during the period besaturated Organic compounds which contain tween repressurihg operation during 3 hours ethylenic unsaturation and which are known to heating is 1300 lbs/sq. in. The reaction vessel art as capable 0f being converted to high is cooled to room temperature, the unreacted pormolecular W ht p lymers, 1. 6., products having tion of the gaseous monomer is bled off and the a degree of polymerization greater than a dimer contents of t e reaction tube are discharged. or m Examples of h u s t m- After drying, 3 parts of polytrifiuoroethylene are Pounds include Vinyl and vmyndene compounds obtained. This polymer is a. solid which does u as vinyl s, i y a etat vi y chlo ide. not melt .at 100 0., but which can be molded a vi yl-fluoride; acrylic and met aery c ac ds into a film at C I and their derivatives such as the esters of lower aliphatic alcohols, e. g., methyl methacrylate, the Example H anhydrides, the amides, and the nitriles; oleflnic A silver-lined high pressure reactor is flushed hydrocarbons, e. g., ethylene, propylene, isobuwith oxygen-free nitrogen and then is charged tylene, styrene, etc,, dienes, butadiene, chloro- 4 softeners, natural resins, or other synthetic resins.

As many apparently widely different embodimerits of this invention'may be made without departing from the spirit and scope thereof, it is to w be understoodl-that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

dium persulfate, potassium persulfate and the like.

The temperatures useful for conducting the polymerization range from 40 to 200 C., depending upon the type of catalyst used. With diacyl peroxide catalysts, temperatures ranging from 60-120 0.; with persulfate catalysts, 'ternperatures ranging from 40-100 (3.; and with dialkyl peroxide, 100-150 C. are generally used. In gen eral, pressures above atmospheric are used.

The polymeric products of thisinvention are of particular advantage in the manufacture of molding plastics, films, foils, fibers, and adhesives. Fibersand films of the polymers of this invention can be used as insulating materials by wrapping the articles to be insulated. Solutions of the polymers can be used for c'oating'wires and coils. Dispersions of the polymers can be readily prepared, .for example, from solutions of the polymers. For many of these purposes, the polymers may be combined or prepared in the presence of plasticizers, stabilizers, fillers, pigments, dyes,

'We claim:

1. A, process for obtaining a solid film-forming moldable polymer consisting of polymeric trifluoroethylene, said process comprising heating at a temperature of 40? C. to 200 C. in contact with a peroxy catalyst under a pressure of from 3000 to'4000 pounds per square inch polymerizable'rno'nomerie material consisting of trifiuoroethylene until said, polymer is obtained.

2. A solid, film-forming, moldable polymer con- ,sisting oi polymeric trifiuoroethylene.

DONALD D. COFFMAN. THOMAS A. FORD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,998,309 Clark Apr. 16, 1935 2,161,078 Mugdan et a1 June 6, 1939 2,334,195 Hopfi Nov. 16, 1943 

